A fully automatic device and method for detecting free chloride ion content of a polymer material

Abstract

The application discloses a kind of full-automatic polymer material free chloride ion content detection device and method, belong to chloride ion content detection technical field.Device includes solid pulverization device (with detachable cutter head), vibrating screening device, extraction device (including weighing, temperature control and magnetic stirring function), suspension separation device and chloride ion detection device.Method steps are as follows: sample is pulverized→0.160-0.315mm particles are screened→extract with pH13-13.5 sodium hydroxide solution according to liquid-solid ratio 10:1→solid-liquid separation is obtained filtrate→nitric acid, mercury thiocyanate and hydrogen peroxide are added to eliminate interference→chloride ion probe detects concentration→free chloride ion content is calculated according to formula.The device realizes full-automatic detection, and by controlling particle size, extraction parameters and interference shielding, the efficiency and accuracy of free chloride ion detection of geopolymer material are significantly improved.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chloride ion content detection, and particularly relates to a full-automatic geopolymer material free chloride ion content detection device and method. BACKGROUND

[0002] Geopolymer materials have important application prospects in the field of marine concrete due to their excellent durability and environmental protection characteristics. Chloride ion erosion is a key factor leading to corrosion of reinforced concrete, and the concentration of free chloride ions (existing in the pore solution in a free state) directly affects the corrosion rate of steel bars. When the concentration of free chloride ions reaches a critical value, it will trigger corrosion of steel bars. Therefore, accurate determination of the free chloride ion content in geopolymer materials is crucial for their durability evaluation.

[0003] The mainstream detection methods for free chloride ion concentration at present include:

[0004] 1. Pore solution pressure filtration method: The pore solution is obtained by extruding the geopolymer sample through high-pressure equipment, and the chloride ion concentration is directly determined. Although this method is recognized as having high accuracy, it has significant defects: special high-pressure filtration molds and pressure equipment are required, which is costly; the operation is complex and requires high skills; the collection of pore solution is difficult, and the results may be deviated due to operation errors.

[0005] 2. Extraction method: Free chloride ions in the sample are extracted by chemical solution for detection. The existing standards (such as ASTM C1218 and RILEM TC 178) are mainly designed for ordinary Portland cement systems, but there are essential differences between geopolymer materials and Portland cement materials:

[0006] Different hydration products: Geopolymer is mainly composed of hydrated sodium aluminum silicate gel (N-A-S-H), while Portland cement material is mainly composed of hydrated calcium silicate gel (C-S-H) and Friedel salt (3CaO·Al2O3·CaCl2·xH2O). There are significant differences in the binding mechanism (physical adsorption vs. chemical binding) and desorption behavior of chloride ions between the two, which leads to doubts about the applicability of the extraction method based on Portland cement systems in geopolymer materials;

[0007] Influence of interfering ions: Geopolymer precursors (such as slag) contain a large amount of sulfides, and the bromide ions (Br - ) introduced by seawater erosion will interfere with the detection of chloride ions, and the existing standards do not provide specific elimination solutions.

[0008] The detection devices and methods disclosed in the prior art also have limitations:

[0009] CN109387415B provides a device by crushing the sample by extrusion, but there are the following problems: low crushing efficiency, only single extrusion, and unable to control the powder particle size, resulting in the difference of specific surface area affecting the consistency of chloride ion leaching rate; without integrating sample weighing and extraction liquid quantification function, liquid-solid ratio is uncontrollable, affecting the accuracy of the results; without setting the solid-liquid separation step, the combined chloride ion in the unfiltered powder continues to desorb during testing, resulting in the free chloride ion concentration detection value being too high.

[0010] CN114518428B proposes a water extraction method for cement-based materials, which is difficult to apply to geopolymer systems: the interference problem of bromine ions and sulfur ions in geopolymer is not solved; the steps are complicated and rely on manual operation, with low automation degree.

[0011] In summary, geopolymer materials lack a dedicated free chloride ion full-automatic detection scheme, and existing methods have deficiencies in accuracy, efficiency and anti-interference ability, so it is urgent to develop an integrated device and method that integrates standardized sample processing, accurate extraction control and interference elimination. SUMMARY

[0012] The purpose of the embodiments of the present application is to provide a full-automatic geopolymer material free chloride ion content detection device and method, which adds nitric acid solution to adjust pH, eliminates alkaline interference, adds mercury thiocyanate solution to mask bromine ions, and adds hydrogen peroxide solution to oxidize sulfur ions, significantly reducing the interference of seawater bromine ions and slag sulfides, thereby overcoming the defects of expensive equipment and complex operation of filter pressing method and multiple interference of extraction method, and further solving at least one technical problem involved in the background art.

[0013] In order to solve the above technical problems, the present application is implemented as follows:

[0014] The embodiments of the present application provide a full-automatic geopolymer material free chloride ion content detection device, which comprises:

[0015] Solid crushing device: comprising a top cover, a first sample inlet, a crushing cavity, a liftable cutter head, a valve and a first sample outlet; the top cover and the first sample inlet are detachably connected; the crushing cavity is arranged at the bottom of the first sample inlet, and four cutter heads with sawteeth are installed at the bottom of the crushing cavity; the first sample outlet is arranged on one side of the bottom of the crushing cavity, and the valve is arranged at the first sample outlet;

[0016] Vibrating screening device: arranged below the solid crushing device, comprising a second sample inlet cooperatively arranged with the first sample outlet, a second sample outlet in communication with the second sample inlet, and a replaceable screen mesh arranged between the second sample inlet and the second sample outlet, the screen mesh aperture limits the particle size to 0.160-0.315mm;

[0017] The extraction device is arranged on one side below the vibrating screening device, and comprises a liquid storage tank, an extraction liquid conduit, a magnetic stirrer, a stirring rod and an extraction container; one end of the extraction liquid conduit is connected with the liquid storage tank, and the other end is connected with the extraction container; the extraction container is arranged below the second sample outlet and above the magnetic stirrer; the stirring rod is arranged in the extraction container; the magnetic stirrer is integrated with a weighing module, a temperature sensor and a heating device, and the stirring speed, the extraction temperature, the extraction time and the liquid mass can be set;

[0018] The suspension separation device is arranged on one side of the extraction device, and comprises a liquid discharge valve, an inclined transmission pipe, a detachable filter screen and a third sample outlet, and the transmission pipe forms an angle with the horizontal plane; the extraction container is connected with one end of the transmission pipe through the liquid discharge valve, and the third sample outlet is arranged at the other end of the transmission pipe; the filter screen is arranged in the transmission pipe;

[0019] The chloride ion detection device is arranged on one side below the third sample outlet of the suspension separation device, and comprises a liquid storage bottle, a first reagent bottle, a second reagent bottle and a third reagent bottle, a liquid adding instrument, a test pool, a chloride ion probe and a chloride ion detection equipment; the liquid adding instrument is connected with the first reagent bottle, the second reagent bottle and the third reagent bottle; the chloride ion probe is connected with the chloride ion detection equipment and is placed in the test pool;

[0020] The display equipment is used for setting parameters, starting and stopping tests and displaying real-time data.

[0021] Optionally, the cutter head of the solid crushing device is detachably connected with the crushing cavity, and a sealing rubber ring is arranged between the top cover and the first sample inlet.

[0022] Optionally, the cutter head is made of stainless steel.

[0023] Optionally, the second sample inlet, the second sample outlet and the screen are made of stainless steel.

[0024] Optionally, the liquid storage tank of the extraction device is made of transparent material and is provided with a solution pump, and the magnetic stirrer controls the liquid-solid ratio to be 10:1.

[0025] Optionally, the extraction container is made of hard plastic material.

[0026] Optionally, the first reagent bottle of the chloride ion detection device contains 0.1 mol / L HNO3 solution, the second reagent bottle contains 0.04% Hg (SCN)2 solution by mass fraction, and the third reagent bottle contains 30% H2O2 solution by mass fraction.

[0027] The application further provides a full-automatic free chloride ion detection method for polymer materials, which adopts the device and comprises the following steps:

[0028] (1) The geopolymer sample with particle size <20 mm is broken by a solid crushing device, and then 0.160-0.315 mm particles are screened by a vibrating screen device;

[0029] (2) A sodium hydroxide extraction solution with pH=13-13.5 is added to an extraction container, the liquid-solid mass ratio is 10:1, the stirring speed is set to 1000 r / min, the extraction temperature is 20°C, and the extraction time is 5 min;

[0030] (3) Solid-liquid separation is performed by a suspension separation device to obtain a filtrate;

[0031] (4) The following is added to the test pool: 10 mL of filtrate, 12-15 mL of 0.1 mol / L HNO3 solution, 1-2 mL of 0.04% Hg(SCN)2 solution, and 3-5 mL of 30% H2O2 solution;

[0032] (5) The chloride ion concentration is detected by a chloride ion probe C 1, unit: mol / L;

[0033] (6) The free chloride ion content is calculated according to the following formula P 1:

[0034] ;

[0035] Wherein V 1 is the volume of the extraction solution, unit: mL; M 1 is the mass of the geopolymer powder particles used for extraction, unit: g.

[0036] Optionally, in step (4), the HNO3 solution is used to adjust the acidity of the filtrate, the Hg(SCN)2 solution is used to eliminate bromide ion interference, and the H2O2 solution is used to eliminate sulfur ion interference.

[0037] Compared with the prior art, the present application has the following advantages:

[0038] 1. The present application adds nitric acid solution (0.1 mol / L) to adjust the pH, eliminates alkaline interference, adds mercury thiocyanate solution (0.04%) to mask bromide ions (forms a stable complex), and adds hydrogen peroxide solution (30%) to oxidize sulfur ions, significantly reducing the interference of seawater bromide ions and slag sulfides.

[0039] 2. The present application strictly limits the extraction parameters (liquid-solid ratio 10:1, particle size 0.160-0.315 mm, temperature 20°C, etc.), solving the error caused by non-uniform parameters in the prior art.

[0040] 3. The present application uses the formula Combined with automatic data input, the reliability of the calculation result is ensured.

[0041] 4、The whole process automation of the application shortens the single detection time to the minute level, significantly improves the efficiency; through the comparison experiment of pressure filtration method, the free chlorine ion detection results of three kinds of geopolymer materials have little deviation, verifying the consistency of the method and the "gold standard".

[0042] 5、The application fills the blank of automatic detection of free chlorine ion of geopolymer material, overcomes the defects of expensive equipment, complex operation and many interferences of extraction method of pressure filtration method; the modular design (such as detachable cutter head, screen) of the device is convenient for maintenance, and is suitable for laboratory and on-site detection. BRIEF DESCRIPTION OF DRAWINGS

[0043] In order to more clearly illustrate the technical solutions in the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiment description. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can also be obtained from these drawings without creative labor, wherein:

[0044] Figure 1 is a schematic diagram of the whole automatic geopolymer material chlorine ion content detection device provided by the embodiment of the application;

[0045] Figure 2 is a schematic diagram of the connection structure of the bottom of the crushing cavity and the cutter head provided by the embodiment of the application;

[0046] Figure 3 is a schematic diagram of the top view structure of the bottom of the crushing cavity and the cutter head provided by the embodiment of the application;

[0047] Figure 4 is a flow chart of the detection of the free chlorine ion content of the geopolymer material provided by the embodiment of the application;

[0048] Figure 5 is a comparison chart of the detection results of the geopolymer material free chlorine ion content detection device of the application and the results of the pressure filtration method provided by the embodiment of the application;

[0049] In the figure: 1, geopolymer sample; 2-1, top cover; 2-2, first sample inlet; 2-3, crushing cavity; 2-4, cutter head, 2-5, valve; 2-6, first sample outlet; 3, vibrating screening device, 3-1, second sample inlet; 3-2, screen; 3-3, second sample outlet; 4-1, liquid storage tank; 4-2, extraction liquid conduit; 4-3, stirring rod; 4-4, extraction container; 4-5, magnetic stirrer; 5-1, liquid discharge valve; 5-2, transmission pipe; 5-3, filter screen; 5-4, third sample outlet; 6-1, liquid storage bottle; 6-2, first reagent supply bottle; 6-3, second reagent supply bottle; 6-4, third reagent supply bottle; 6-5, liquid adding instrument; 6-6, test cell; 6-7, chloride ion probe; 6-8, chloride ion test equipment; 7, display equipment. DETAILED DESCRIPTION

[0050] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are some of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application.

[0051] The terms "first", "second" and the like in the specification of the present application are used to distinguish similar objects, and are not used to describe a specific order or sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application can be implemented in an order other than those illustrated or described herein, and the objects distinguished by "first", "second" and the like are generally of a kind and are not limited in number, for example, the first object can be one or more. In addition, "and / or" in the specification means at least one of the connected objects, and the character " / ", generally means that the front and rear associated objects are in an "or" relationship.

[0052] Please refer to Figure 1 As shown in the figure, the embodiments of the present application provide a full-automatic geopolymer material free chloride ion content detection device, which comprises a solid crushing device, a vibrating screening device 3, an extraction device, a suspension separation device, a chloride ion detection device and a display equipment 7 connected in sequence.

[0053] The solid crushing device is used for crushing the geopolymer sample 1, and comprises a top cover 2-1, a first sample inlet 2-2, a crushing cavity 2-3, a liftable cutter head 2-4, a valve 2-5 and a first sample outlet 2-6.

[0054] The top cover 2-1 and the first sample inlet 2-2 are of suitable size and are detachably connected.

[0055] The top cover 2-1 is provided with a sealing rubber ring between the first sample inlet 2-2, which can ensure the sealing and prevent the sample from splashing out of the solid crushing device.

[0056] The first sample inlet 2-2 is conical, funnel-shaped or other shapes as long as the side wall is inclined.

[0057] The crushing cavity 2-3 is arranged at the bottom of the first sample inlet 2-2, and the crushing cavity 2-3 is made of stainless steel, which can ensure sufficient strength and anti-rust function, and can protect the sample from being contaminated during crushing.

[0058] The shape of the crushing cavity 2-3 is cylindrical, which can ensure that the sample can be completely crushed.

[0059] The bottom of the crushing cavity 2-3 is inclined, so that the crushed powder can enter the vibrating screening device 3 through the first sample outlet 2-6.

[0060] In combination with Figure 2 and Figure 3 It is shown that the crushing cavity 2-3 is provided with four cutter heads 2-4 with sawteeth at the bottom, the cutter heads 2-4 are made of stainless steel, and are detachably connected with the crushing cavity 2-3.

[0061] The cutter heads 2-4 can be lifted and lowered, which can ensure that the crushed sample can be poured out from the bottom of the crushing cavity 2-3.

[0062] The first sample outlet 2-6 is arranged at one side of the bottom of the crushing cavity 2-3, and the valve 2-5 is arranged in the first sample outlet 2-6.

[0063] The vibrating screening device 3 can set the vibrating screening time, including the second sample inlet 3-1 cooperated with the first sample outlet 2-6, the second sample outlet 3-3 communicated with the second sample inlet 3-1, and the replaceable screen 3-2 arranged between the second sample inlet 3-1 and the second sample outlet 3-3, the aperture of the screen 3-2 is limited to 0.160-0.315mm.

[0064] The second sample inlet 3-1 should ensure sufficient diameter to ensure that the crushed sample can completely enter the vibrating screening device 3.

[0065] The materials of the second sample inlet 3-1, the second sample outlet 3-3 and the screen 3-2 are all stainless steel.

[0066] The extraction device is arranged below one side of the vibrating screening device 3, including a liquid storage tank 4-1, an extraction liquid conduit 4-2, a magnetic stirrer 4-5, a stirring rod 4-3 and an extraction container 4-4.

[0067] The liquid storage tank 4-1 stores the extraction liquid for testing and needs to have alkali resistance. The liquid storage tank 4-1 is equipped with a liquid inlet pump that can quantitatively output the liquid mass, and the liquid inlet pump is electrically connected with the controller.

[0068] The liquid storage tank 4-1 should be made of transparent material to facilitate observation of the content of the extraction liquid and facilitate timely replenishment.

[0069] One end of the extraction liquid conduit 4-2 is connected with the liquid storage tank 4-1, and the other end is connected with the extraction container 4-4.

[0070] The material of the extraction liquid conduit 4-2 needs to have alkali resistance, and its function is to input the extraction liquid from the liquid storage tank 4-1 into the extraction device.

[0071] The stirring rod 4-3 is arranged in the extraction container 4-4 and has magnetism, and the stirring rod 4-3 is driven to rotate by a magnetic field to stir the extraction liquid. Further, the stirring rod 4-3 has alkali resistance and high temperature resistance.

[0072] The extraction container 4-4 is arranged below the second sample outlet 3-3 and above the magnetic stirrer 4-5, and the material of the extraction container 4-4 is hard plastic material and has alkali resistance and high temperature resistance.

[0073] The magnetic stirrer 4-5 integrates a weighing module, a temperature sensor and a heating device, and can set the stirring speed, the extraction temperature, the extraction time and the liquid mass, and is used for controlling the liquid-solid ratio to be 10:1.

[0074] In general, the extraction device can control the parameters such as the extraction time (5 min), the stirring speed (1000 r / min), the extraction temperature (20℃) and the liquid mass of the extraction liquid (10 times the mass of the screened powder), and ensure the consistency of the extraction parameters in the free chloride ion test, thereby improving the reliability of the test results.

[0075] The suspension separation device is installed on one side of the extraction device and includes a liquid discharge valve 5-1, an inclined transmission pipe 5-2, a detachable filter screen 5-3 and a third sample outlet 5-4.

[0076] The material of the liquid discharge valve 5-1 and the transmission pipe 5-2 has alkali resistance.

[0077] The transmission pipe 5-2 forms an angle with the horizontal plane and has a certain slope, so that the filtrate can enter the filtrate storage bottle 6-1 from the third sample outlet 5-4 by gravity.

[0078] One end of the extraction container 4-4 and the transmission pipe 5-2 is connected through the liquid discharge valve 5-1, and the third sample outlet 5-4 is arranged at the other end of the transmission pipe 5-2.

[0079] The filter screen 5-3 is arranged in the transmission pipe 5-2, and the shape is not limited as long as the filtrate and the powder can be separated.

[0080] The filter screen 5-3 is detachably connected with the transmission pipe 5-2, which facilitates the cleaning of the powder solid after filtration.

[0081] One side of the outlet of the transmission pipe 5-2 is connected with the third sample outlet 5-4, and the filter screen 5-3 is arranged on one side of the transmission pipe 5-2.

[0082] The chloride ion detection device is arranged on one side below the third sample outlet 5-4 of the suspension separation device, so that the filtrate can be completely introduced into the storage bottle 6-1. The chloride ion detection device comprises the storage bottle 6-1, a liquid adding instrument 6-5, a test pool 6-6, a chloride ion probe 6-7 and a chloride ion detection equipment 6-8.

[0083] The storage bottle 6-1 has alkali resistance, and the filtrate is alkaline, so the storage bottle 6-1 needs to be prevented from being corroded.

[0084] The liquid adding instrument is connected with the first reagent bottle 6-2, the second reagent bottle 6-3 and the third reagent bottle 6-4, and the liquid adding instrument can quantitatively add liquid into the test pool 6-6, so as to avoid the error of manual measurement and improve the precision of subsequent detection.

[0085] The chloride ion probe 6-7 is arranged in the test pool 6-6, and the chloride ion concentration can be measured by the chloride ion detection equipment 6-8.

[0086] The first reagent bottle 6-2 of the chloride ion detection device contains 0.1 mol / L HNO3 solution, the second reagent bottle 6-3 contains 0.04% mass fraction Hg (SCN) 2 solution, and the third reagent bottle 6-4 contains 30% mass fraction H2O2 solution.

[0087] The display equipment 7 is used for setting parameters, starting and stopping testing and displaying real-time data. Specifically, the display equipment 7 has real-time display of testing process, setting parameters and testing data, including sample mass, extraction time and free chloride ion content. The display equipment can make the operator easily check the current testing state through a friendly user interface, and monitor the key parameters at any time during the testing process.

[0088] The application also provides a full-automatic polymer material free chloride ion detection method, which adopts the device and comprises the following steps.

[0089] (1) The geopolymer sample with a particle size of less than 20 mm is broken by a solid crushing device, and then the 0.160-0.315 mm particles are screened by a vibrating screen device.

[0090] (2) adding sodium hydroxide extraction solution with pH = 13-13.5 into the extraction container, liquid-solid mass ratio 10:1, setting 1000 r / min stirring speed, 20℃ extraction temperature and 5 min extraction time;

[0091] (3) solid-liquid separation through the suspension separation device to obtain the filtrate;

[0092] (4) adding into the test pool: 10 mL of the filtrate, 12-15 mL of 0.1 mol / L HNO3 solution, 1-2 mL of 0.04% Hg(SCN)2 solution in mass fraction, 3-5 mL of 30% H2O2 solution in mass fraction;

[0093] (5) detecting the chloride ion concentration by the chloride ion probe C 1, unit: mol / L;

[0094] (6) calculating the free chloride ion content according to the following formula P 1:

[0095]

[0096] wherein V 1 is the extraction liquid volume, unit: mL; M 1 is the powder mass, unit: g.

[0097] In step (4), the HNO3 solution is used for adjusting the filtrate acidity, the Hg(SCN)2 solution is used for eliminating bromide ion interference, and the H2O2 solution is used for eliminating sulfur ion interference.

[0098] The following will describe the full-automatic polymeric material free chloride ion detection method provided by the present application in detail by specific embodiments.

[0099] Embodiment 1

[0100] In combination with Figure 1 the drawings, the present embodiment 1 provides a full-automatic polymeric material free chloride ion detection method, which comprises the following steps:

[0101] (1) preparing the polymeric material sample solid 1, opening the top cover 2-1, putting the polymeric material sample 1 (diameter less than 20 mm and height less than 20 mm) into the crushing cavity 2-3 through the first sample inlet 2-2, confirming that the cutter head 2-4 is in the lowest state and checking that the valve 2-5 has fallen down. Covering the top cover 2-1, then setting the crushing time of the solid crushing device on the display device 7, and starting the solid crushing. After the polymeric sample crushing is completed, starting the valve 2-5 falling down on the display device 7, at this time the cutter head 2-4 is raised, the valve 2-5 is raised, and the powder sample is poured out from the powder first sample outlet 2-6 along the inclined bottom into the vibration screening device 3. ​

[0102] (2) Prepare the sample for the sieve shaker, make sure that the powder sample has been put into the sieve shaker 3, and set the time for the sieve shaker on the display device 7. Start the sieve shaker 3, and the powder sample will be separated into the corresponding particle size through the sieve 3-2, and the sample of the corresponding particle size will be poured into the extraction container 4-4 through the second sieve outlet 3-3 during the shaking process.

[0103] (3) Prepare for the extraction, check that the solution pump is connected to the solution tank 4-1, and connect the solution pump to the extraction container 4-4 through the solution pipe, and make sure that the solution supply system is unobstructed. Make sure that the liquid discharge valve 5-1 is closed to ensure that the extraction container wall is closed during the extraction process. After the powder sample is put into the extraction container 4-4, check the mass of the powder sample on the display device 7, and then set the extraction parameters on the display device 7, including the extraction time (5 min), the stirring speed (1000 r / min), the extraction temperature (20℃), and the mass of the extraction solution (10 times the mass of the sieved powder). After setting all the parameters, start the extraction device, start the solution tank 4-1, and add the extraction solution according to the liquid-solid ratio of the test method, and the extraction solution is added into the extraction container 4-4 through the extraction solution pipe 4-2.

[0104] (4) After the extraction is completed, open the liquid discharge valve 5-1 to filter the liquid, and the extraction container 4-4 is connected to the transmission pipe 5-2 through the liquid discharge valve 5-1, and the liquid discharge valve 5-1 is closed during the extraction process. When in the filtering state, the liquid discharge valve 5-1 is opened to facilitate the mixed liquid of the powder and the extraction solution to pass through the transmission pipe 5-2. The mixed liquid of the powder sample and the extraction solution passes through the transmission pipe 5-2, and the powder sample is intercepted in the transmission pipe 5-2 by the filter screen 5-3.

[0105] (5) After the filtrate is put into the solution bottle 6-1, the free chlorine ion test is carried out in the test pool, and 10 mL of the filtrate is quantitatively added from the solution bottle 6-1 to the test pool through the liquid adding instrument 6-5; 12-15 mL of 0.1 mol / L HNO3 solution is quantitatively added from the first reagent supply bottle to the test pool; 1-2 mL of Hg (SCN)2 with a solute mass fraction of 0.04% is quantitatively added from the second reagent supply bottle to the test pool; and 3-5 mL of H2O2 solution with a solute mass fraction of 30% is quantitatively added from the third reagent supply bottle to the test pool. Set the start of the chlorine ion test on the display device 7, and carry out the chlorine ion test through the chlorine ion probe 6-7 in the test pool 6-6, and carry out the chlorine ion detection through the chlorine ion test device 6-8 connected to the chlorine ion probe 6-7. The display device 7 can display the data of the free chlorine ion content and can store the data.

[0106] (6) Equipment maintenance and cleaning after testing After the test is completed, turn off the power and disconnect the connection. Clean the powder samples from the vibration screening device 3 and the residual powder samples in the transmission pipe 5-2, and perform necessary cleaning and maintenance of the equipment. Check the working condition of all devices to ensure that the equipment can work normally in the next test.

[0107] Example 2

[0108] The specific steps of the test method for testing the free chloride content of geopolymer materials using the measuring device of this embodiment 2 are as follows:

[0109] Actual tests were performed by the fully automatic geopolymer material free chloride content detection device, and the results were compared and analyzed with the traditional pressure filtration method to verify the accuracy of the device in testing the free chloride content.

[0110] 1. Purpose of the experiment

[0111] The main purpose of Example 2 is to evaluate the actual performance of the fully automatic geopolymer material free chloride content detection device and compare it with the traditional pressure filtration method.

[0112] 2. Experimental device and geopolymer material sample

[0113] The fully automatic geopolymer material free chloride detection experimental device uses Figure 1 The pressure filtration method measuring device includes a pressure filtration mold, a press, and a chloride ion tester, etc.

[0114] The geopolymer material sample is added in the form of internally doped chloride ions to the geopolymer material, and then the free chloride content is detected at different ages (3 days, 7 days, and 28 days). Set 3 groups of geopolymer material test samples with different slag and fly ash ratios, and at the same time, use the pressure filtration method to detect the free chloride concentration as a control.

[0115] The mix proportion of the test sample is: the precursors of the geopolymer material are slag and fly ash, with a slag / fly ash ratio of 100 / 0, 75 / 25, and 50 / 50, respectively, denoted as FA-0, FA-25, and FA-50; the activator is sodium hydroxide and water glass; the activator modulus (Ms = SiO2 / Na2O) is 1.0, and the activator alkalinity is 6wt.% Na2O; the chloride ion dosage is 0.5%, 1%, and 2% of the cementitious material, respectively; and the water-binder ratio is 0.4.

[0116] 3. Determination steps using the fully automatic device of the present application

[0117] Referring to Figure 4 After reaching the test age, the geopolymer material free chloride content test embodiment of the present application is performed according to the following steps:

[0118] (1) Start the full-automatic device, add the geopolymer block sample into the solid crushing device, set the crushing time through the display equipment, carry out the solid crushing, open the valve after the crushing is completed, and discharge the powder into the vibrating screening device.

[0119] (2) Select the screen mesh with 55 mesh and 90 mesh, set the vibrating screening time, carry out the vibrating screening after the solid crushing, and obtain the powder particles with the particle size diameter of 0.16-0.315 mm.

[0120] (3) According to the mass of the powder particles after the screening, set the sodium hydroxide extraction liquid (pH=13-13.5) with 10 times the mass of the powder. The extraction parameters of the extraction device are that the stirring speed is 1000 r / min, the stirring time is 5 min, and the extraction temperature is 20℃. Finally, start the extraction device to carry out the extraction.

[0121] (4) After the extraction is completed, open the liquid discharge valve, separate the suspension to obtain the filtrate, and then quantitatively add 10 mL of the filtrate, 12-15 mL of 0.1 mol / L of HNO3, 1-2 mL of the Hg(SCN)2 solution with the solute mass fraction of 0.04% and 3-5 mL of the H2O2 solution with the solute mass fraction of 30% through the liquid adding instrument to eliminate the influence of interference ions, then carry out the chlorine ion test in the test cell to obtain the free chlorine ion concentration, and record and save the data.

[0122] (5) According to the free chlorine ion concentration obtained by the test, calculate the free chlorine ion content in the geopolymer material to be tested through formula (1) P 1(%).

[0123] (1)

[0124] In the formula, P 1(%) is the content of the free chlorine ion in the geopolymer material; C 1(mol / L) is the chlorine ion concentration measured by the chlorine ion detection equipment in step (4), V 1(mL) is the volume of the filtrate obtained in step (3), which is also the volume of the extraction liquid quantitatively added in step (3), M 1(g) is the mass of the geopolymer powder particles obtained after the screening in step (2) for extraction, and 0.03545 is the millimole mass of chlorine ion g / mmol.

[0125] (6) Equipment cleaning and maintenance:

[0126] After the test is completed, turn off the equipment, clean the test device, and carry out the routine maintenance of the equipment.

[0127] 4. Test steps of the pressure filtration method

[0128] (1) Weigh the geopolymer material after it has reached the designed curing age, then crush it and put it into a filter press mold. Place the filter press mold on a press to load it and obtain the pore solution of the geopolymer material.

[0129] (2) After obtaining the pore solution, filter it with a needle filter, measure the volume of the pore solution, and then store it in time and seal it.

[0130] (3) Connect a chloride ion probe to a chloride ion testing device to test the chloride ion concentration of the pore solution. If the pore solution content is low, it can be diluted before testing. The free chloride ion content in the pore solution obtained by pore solution pressure filtration can be calculated using formula (2):

[0131] (2)

[0132] In the formula, P 2 (%) represents the chloride ion content of the pore solution obtained by pressure filtration of the geopolymer material. C 2 (mol / L) represents the chloride ion concentration of the pore solution obtained in step (3). V 2 (mL) of the solution volume obtained in step (2) M 2 (g) is the mass of the geopolymer material used for pressure filtration in step (1), and 0.03545 is the millimole mass of chloride ions in g / mmol.

[0133] 5. Comparison of Experimental Results

[0134] pass Figure 5 The experimental results clearly show that, in comparison with the data obtained by the method of this invention (extraction solution of sodium hydroxide with pH 13-13.5, liquid-solid ratio of 10 / 1, particle size controlled at 0.16-0.315 mm, water extraction time of 5 min, extraction stirring speed of 1000 r / min, extraction temperature of 20 °C) and pore solution pressure filtration method, it can be determined that the free chloride ion content obtained by the detection method provided by this invention is very close to and basically consistent with the data obtained by the pore solution pressure filtration method.

[0135] It should be noted that, in this document, the terms "comprising," "including," or any other variations thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or system that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process, method, article, or system. Unless otherwise specified, an element defined by the phrase "comprising one..." does not exclude the presence of other identical elements in the process, method, article, or system that includes that element.

[0136] Furthermore, it is to be understood that the scope of the methods and systems of the present application are not limited to performing functions in the order discussed or illustrated, nor are they limited in scope to only performing the functions described in the description. The methods described can be performed in other orders or simultaneously, and the steps described can be added, omitted or combined. Furthermore, features described in relation to certain examples can be combined in other examples.

[0137] The above embodiments of the present application have been described in conjunction with the accompanying drawings, but the present application is not limited to the above described embodiments, and the above described embodiments are merely illustrative, not restrictive, and those skilled in the art can make many forms under the inspiration of the present application without departing from the purpose of the present application and the scope of protection, which are all within the protection of the present application.

Claims

1. A fully automated device for detecting free chloride ion content of a polymer material, characterized by, The application relates to a solid pulverizing device, a vibrating screening device, an extraction device and a suspension separating device. The solid pulverizing device comprises a top cover (2-1), a first sample inlet (2-2), a pulverizing cavity (2-3), liftable cutter heads (2-4), a valve (2-5) and a first sample outlet (2-6); the top cover (2-1) and the first sample inlet (2-2) are detachably connected; the pulverizing cavity (2-3) is arranged at the bottom of the first sample inlet (2-2), and four cutter heads (2-4) with sawteeth are arranged at the bottom of the pulverizing cavity (2-3); the first sample outlet (2-6) is arranged at one side of the bottom of the pulverizing cavity (2-3), and the valve (2-5) is arranged at the first sample outlet (2-6); The vibrating screening device (3) is arranged below the solid pulverizing device and comprises a second sample inlet (3-1) matched with the first sample outlet (2-6), a second sample outlet (3-3) communicated with the second sample inlet (3-1) and a replaceable screen (3-2) arranged between the second sample inlet (3-1) and the second sample outlet (3-3); the screen (3-2) is provided with holes with a particle size of 0.160-0.315 mm; The extraction device is arranged at one side below the vibrating screening device (3) and comprises a liquid storage tank (4-1), an extraction liquid conduit (4-2), a magnetic stirrer (4-5), a stirring rod (4-3) and an extraction container (4-4); one end of the extraction liquid conduit (4-2) is connected with the liquid storage tank (4-1), and the other end is connected with the extraction container (4-4); the extraction container (4-4) is arranged below the second sample outlet (3-3) and above the magnetic stirrer (4-5); the stirring rod (4-3) is arranged in the extraction container (4-4); the magnetic stirrer (4-5) is integrated with a weighing module, a temperature sensor and a heating device, and the stirring speed, the extraction temperature, the extraction time and the liquid mass can be set; The suspension separating device is arranged at one side of the extraction device and comprises a liquid discharge valve (5-1), an inclined transmission pipe (5-2), a detachable filter screen (5-3) and a third sample outlet (5-4); the transmission pipe (5-2) forms an angle with the horizontal plane; the extraction container (4-4) is connected with one end of the transmission pipe (5-2) through the liquid discharge valve (5-1), and the third sample outlet (5-4) is arranged at the other end of the transmission pipe (5-2); the filter screen (5-3) is arranged in the transmission pipe (5-2). Chloride ion detection device: installed in the third sample port (5-4) below the suspension separation device on one side, including the liquid storage bottle (6-1), the first reagent bottle (6-2), the second reagent bottle (6-3) and the third reagent bottle (6-4), the liquid adding instrument (6-5), the test pool (6-6), the chloride ion probe (6-7) and the chloride ion detection equipment (6-8); the liquid adding instrument (6-5) is connected with the first reagent bottle (6-2), the second reagent bottle (6-3) and the third reagent bottle (6-4); the chloride ion probe (6-7) is connected with the chloride ion detection equipment (6-8) and placed in the test pool (6-6); the first reagent bottle (6-2) of the chloride ion detection device contains 0.1 mol / L HNO3 solution, the second reagent bottle (6-3) contains 0.04% mass fraction Hg(SCN)2 solution, and the third reagent bottle (6-4) contains 30% mass fraction H2O2 solution; Display device (7): for setting parameters, starting and stopping tests and displaying real-time data.

2. The apparatus of claim 1, wherein, The cutter head (2-4) of the solid crushing device is detachably connected with the crushing cavity (2-3), and a sealing rubber ring is arranged between the top cover (2-1) and the first sample inlet (2-2).

3. The apparatus of claim 1, wherein, The cutter head (2-4) is made of stainless steel.

4. The apparatus of claim 1, wherein, The second sample inlet (3-1), the second sample outlet (3-3) and the screen (3-2) are all made of stainless steel.

5. The apparatus of claim 1, wherein, The liquid storage tank (4-1) of the extraction device is made of transparent material and is equipped with a solution pump, and the magnetic stirrer (4-5) controls the liquid-solid ratio to be 10:

1.

6. The apparatus of claim 1, wherein, The material of the extraction container (4-4) is hard plastic material.

7. A fully automated method for detecting free chloride ions in a polymer material, characterized in that The device of any one of claims 1-6 is used, comprising the following steps: (1) crushing the geopolymer sample with a particle size of less than 20 mm by the solid crushing device, and screening 0.160-0.315 mm particles through the vibrating screening device; (2) adding sodium hydroxide extraction solution with pH=13-13.5 into the extraction container, with a liquid-solid mass ratio of 10:1, setting the stirring speed to 1000 r / min, the extraction temperature to 20°C and the extraction time to 5 min; (3) performing solid-liquid separation by the suspension separation device to obtain the filtrate; (4) adding 10 mL of the filtrate, 12-15 mL of 0.1 mol / L HNO3 solution, 1-2 mL of 0.04% mass fraction Hg(SCN)2 solution and 3-5 mL of 30% mass fraction H2O2 solution into the test pool; (5) detecting chloride ion concentration with a chloride ion probe C 1; (6) The free chloride ion content is calculated according to the following formula P 1: ； wherein V 1 is the volume of the extraction liquid; M 1 is the mass of the geopolymer powder particles used for the extraction.

8. The method of claim 7, wherein, In step (4), the HNO3 solution is used to adjust the acidity of the filtrate, the Hg(SCN)2 solution is used to eliminate bromide ion interference, and the H2O2 solution is used to eliminate sulfur ion interference.

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